CN103601316A - Harmless treatment method for contaminated soil eluate - Google Patents
Harmless treatment method for contaminated soil eluate Download PDFInfo
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- CN103601316A CN103601316A CN201310569690.8A CN201310569690A CN103601316A CN 103601316 A CN103601316 A CN 103601316A CN 201310569690 A CN201310569690 A CN 201310569690A CN 103601316 A CN103601316 A CN 103601316A
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- contaminated soil
- soil
- elutant
- thiacalixarene
- heavy metal
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Abstract
The invention discloses a harmless treatment method for contaminated soil eluate and relates to contaminated soil treatment methods. The method comprises the following processes: adjusting the pH value of sulfonated thiacalixarene eluting eluate of heavy metal contaminated soil to be 12 by using sodium hydroxide; adding sodium sulfide according to the mole concentration ratio of sodium sulfide/sulfonated thiacalixarene of 2: 1, stirring for 10 minutes by using a stirrer, mixing uniformly to completely dissolve sodium sulfide, then standing for 24 hours; putting the eluate in a centrifuge tube, and carrying out centrifugation for 10 minutes at the rate of 5,000 r/min, so as to obtain a supernatant; adding concentrated nitric acid into the supernatant, and adjusting the pH value to be 10, thereby recycling the eluate as an eluent for repairing the heavy metal contaminated soil. The method has the advantages that the sulfonated thiacalixarene eluting eluate of the heavy metal contaminated soil can be subjected to harmless treatment, the recycling of the sulfonated thiacalixarene eluent is realized, the soil repair cost is reduced greatly, and the operating steps are simple, convenient and easy in implementation.
Description
Technical field
The present invention relates to a kind of contaminated soil treatment process, particularly relate to a kind of method for innocent treatment of contaminated soil elutant.
Background technology
In recent years, along with the continuous quickening of China's industrialization and urbanization process, Soil Environmental Pollution problem is increasingly serious, and Sustainable Use of Soil Resources and agricultural-food ecological safety have been formed to grave danger.According to data, the soil of China's heavy metal contamination approximately 2,000 ten thousand hm
2, account for 1/6 left and right of total cultivated area, every year because the grain of heavy metal contamination is more up to millions of tons.Therefore, the repairing and treating of heavy-metal contaminated soil has become the vital task of China's ecological environmental protection.
Current, countries in the world all take much count of heavy metal contamination Research on Treatment, and carry out research work widely.According to the difference of administering technique and principle, contaminated soil is administered technology and can be divided into: engineering control measure and physical chemistry are repaired two large classes.Engineering control measure mainly comprises: soil moved in to improve the original, soil removal and replacement, go to show soil and the deep ploughing measure such as dig; Physical chemistry reparation mainly comprises: curing/stabilizing, electronic reparation, drip washing reparation, redox, biological restoration etc.Compare with other restorative procedures, Soil leaching recovery technique has stable treatment effect, advantage thoroughly, has now become one of the focus of heavy-metal contaminated soil fast repair technique research and developing direction.
The drip washing recovery technique of heavy-metal contaminated soil is a recovery technique that depends on water, lessivation makes heavy metal contaminants from solid phase soil, transfer in liquid phase leacheate, a large amount of elutants have been produced, if its direct outer row not only can be caused to the wasting of resources, but also can increase the weight of processing load and the difficulty of sewage works.Therefore to be that can Soil leaching renovation technique clean harmless, the key of economical and efficient operation, how to realize the harmless treatment of heavy-metal contaminated soil drip washing elutant and reuse.
Sulfonation Thiacalixarene is the agent of a kind of supramolecule Soil leaching, the lower of it can be by the collaborative coordination of phenol hydroxyl Sauerstoffatom and bridging sulphur atom complexing heavy metal optionally along molecule cavity, it close to EDTA, is a kind of new soil eluent that has very much application potential to the complex ability of heavy metal Cd, Pb, Cu.But this compound not yet enters the suitability for industrialized production stage at present, rehabilitation cost is relatively high, if the heavy metal in contaminated soil elutant is carried out to harmless treatment, realize the cyclically utilizing of elutant, to greatly reduce rehabilitation cost, and make sulfonation Thiacalixarene drip washing recovery technique move towards the practical possibility that becomes.
Summary of the invention
The object of the present invention is to provide a kind of method for innocent treatment of contaminated soil elutant, the method is carried out harmless treatment by heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant, realize the cyclically utilizing of sulfonation Thiacalixarene leacheate, reduce soil remediation cost, simple operating steps, easily capable.
The object of the invention is to be achieved through the following technical solutions:
A method for innocent treatment for contaminated soil elutant, described method comprises following process: it is 12 that above-mentioned heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant is adjusted to pH value with sodium hydroxide; In [sodium sulphite]/[sulfonation Thiacalixarene] volumetric molar concentration ratio, be that 2:1 adds sodium sulphite, with agitator, stir 10 minutes, mix, sodium sulphite is all dissolved, then standing 24 hours; Elutant is placed in to centrifuge tube, under 5000 revs/min of speed centrifugal 10 minutes, obtains supernatant liquor; In supernatant liquor, add concentrated nitric acid, pH value is adjusted to 10, the leacheate that can be used as restoration of soil polluted by heavy metal carries out cyclically utilizing.
The method for innocent treatment of described a kind of contaminated soil elutant, described heavy metal in soil content is: Cd 8.23 mg/kg, Pb 1069.79 mg/kg, Cu 476.60 mg/kg; Take this soil of 100g and join in triangular flask, add sulfonation Thiacalixarene solution 1000 ml of 5 mmol/L, 180 rpm vibrations 12 hours, centrifugal, get supernatant liquor, be heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant.
Advantage of the present invention and effect are:
The present invention can carry out harmless treatment by heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant, realizes the cyclically utilizing of sulfonation Thiacalixarene leacheate, greatly reduces soil remediation cost, simple operating steps, easily capable.In above-mentioned heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant, Cd, Pb, Cu tri-heavy metal species content are reduced to respectively 0.039 mg/L, 0.28mg/L, 0.32mg/L after measured, clearance is respectively Cd 95%, Pb 99%, Cu 93%, and in elutant, heavy metal content meets China's integrated wastewater discharge standard.
Embodiment
Below in conjunction with illustrated embodiment, the invention will be further described.
Treating processes of the present invention:
1. heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant being adjusted to pH value with sodium hydroxide is 13;
2. in [sodium sulphite]/[sulfonation Thiacalixarene] volumetric molar concentration ratio, be that 1:1～5:1 adds sodium sulphite, with agitator, stir 10 minutes, mix, sodium sulphite is all dissolved, then standing 24 hours;
3. elutant is placed in to centrifuge tube, under 5000 revs/min of speed centrifugal 10 minutes, obtains supernatant liquor;
4. in supernatant liquor, add concentrated nitric acid, pH value is adjusted to 7～11, the leacheate that can be used as restoration of soil polluted by heavy metal carries out cyclically utilizing.
It is 13 that the present invention requires to use sodium hydroxide that sulfonation Thiacalixarene soil elutant is adjusted to pH value, object is to make along four phenolic hydroxyl groups, to ionize completely under sulfonation Thiacalixarene molecule, in its molecule, phenyl ring unit overturns, its molecular conformation is converted to 1 by being beneficial to the vertebra formula conformation (cone) that forms complex compound with heavy metal, 3-replaces (1,3-alternate), 1,2-replaces (1,2-alternate), part vertebra formula (part-cone) etc. is unfavorable for and heavy metal forms the conformation of complex compound, makes heavy metal and sulfonation Thiacalixarene releasing complexing action.The object that adds sodium sulphite in the present invention is to make heavy metal and sodium sulphite generation chemical reaction, generates sulfide precipitation, thereby can adopt centrifugal method that heavy metal is separated from elutant.By the pH value of sodium hydroxide adjustment elutant, be then 7～11, make sulfonation Thiacalixarene molecule recover heavy metal complex ability, can again as leached soil solutions, carry out cyclically utilizing.
Embodiment 1:
Contaminated soil is collected in resettlement district, smeltery, Shenyang.Heavy metal in soil content is: Cd 8.23 mg/kg, Pb 1069.79 mg/kg, Cu 476.60 mg/kg.Take this soil of 100g and join in triangular flask, add sulfonation Thiacalixarene solution 1000 ml of 5 mmol/L, 180 rpm vibrations 12 hours, centrifugal, get supernatant liquor, be heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant.In this elutant, heavy metal content is after measured: Cd 0.78mg/L, Pb 74.80mg/L, Cu 4.57mg/L.
Claims (2)
1. a method for innocent treatment for contaminated soil elutant, is characterized in that, described method comprises following process: it is 12 that above-mentioned heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant is adjusted to pH value with sodium hydroxide; In [sodium sulphite]/[sulfonation Thiacalixarene] volumetric molar concentration ratio, be that 2:1 adds sodium sulphite, with agitator, stir 10 minutes, mix, sodium sulphite is all dissolved, then standing 24 hours; Elutant is placed in to centrifuge tube, under 5000 revs/min of speed centrifugal 10 minutes, obtains supernatant liquor; In supernatant liquor, add concentrated nitric acid, pH value is adjusted to 10, the leacheate that can be used as restoration of soil polluted by heavy metal carries out cyclically utilizing.
2. the method for innocent treatment of a kind of contaminated soil elutant according to claim 1, is characterized in that, described heavy metal in soil content is: Cd 8.23 mg/kg, Pb 1069.79 mg/kg, Cu 476.60 mg/kg; Take this soil of 100g and join in triangular flask, add sulfonation Thiacalixarene solution 1000 ml of 5 mmol/L, 180 rpm vibrations 12 hours, centrifugal, get supernatant liquor, be heavy-metal contaminated soil sulfonation Thiacalixarene drip washing elutant.
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| CN201310569690.8A CN103601316B (en) | 2013-11-13 | 2013-11-13 | Harmless treatment method for contaminated soil eluate |
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| CN201310569690.8A CN103601316B (en) | 2013-11-13 | 2013-11-13 | Harmless treatment method for contaminated soil eluate |
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| CN103601316B CN103601316B (en) | 2014-12-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230120A (en) * | 2014-09-29 | 2014-12-24 | 中国电建集团中南勘测设计研究院有限公司 | Integrated treating and reusing device for heavy metal chemical leaching liquid waste and method for treating and reusing leaching liquid |
| CN109721146A (en) * | 2019-01-31 | 2019-05-07 | 环境保护部华南环境科学研究所 | Heavy metal chelating agent for wastewater treatment |
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| CN101559350A (en) * | 2009-05-15 | 2009-10-21 | 沈阳大学 | Water pollutant adsorption resin and preparation method thereof |
| CN101811133A (en) * | 2010-04-27 | 2010-08-25 | 河海大学 | Ultrasonic remediating method for heavy metal polluted soil/slurry |
| CN102188951A (en) * | 2011-05-13 | 2011-09-21 | 沈阳大学 | Water body pollutant adsorbing material |
| CN102815805A (en) * | 2011-06-08 | 2012-12-12 | 工信华鑫科技有限公司 | Treatment process method of waste water containing nickel and copper ions |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2004101260A (en) * | 2004-01-20 | 2005-06-20 | Федеральное государственное унитарное предпри тие " Всероссийский научно-исследовательский институт неорганических материалов имени акдемика А.А. Бочарова" (RU) | METHOD FOR CLEANING SOILS AND SOILS FROM RADIONUCLIDES AND HEAVY METALS |
| CN101559350A (en) * | 2009-05-15 | 2009-10-21 | 沈阳大学 | Water pollutant adsorption resin and preparation method thereof |
| CN101811133A (en) * | 2010-04-27 | 2010-08-25 | 河海大学 | Ultrasonic remediating method for heavy metal polluted soil/slurry |
| CN102188951A (en) * | 2011-05-13 | 2011-09-21 | 沈阳大学 | Water body pollutant adsorbing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104230120A (en) * | 2014-09-29 | 2014-12-24 | 中国电建集团中南勘测设计研究院有限公司 | Integrated treating and reusing device for heavy metal chemical leaching liquid waste and method for treating and reusing leaching liquid |
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| CN109721146A (en) * | 2019-01-31 | 2019-05-07 | 环境保护部华南环境科学研究所 | Heavy metal chelating agent for wastewater treatment |
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